AMINES
1
AMINES INTRODUCTION In this unit we shall focus our attention on the chemistry of organic compounds with functional groups containing nitrogen. The important functional groups in which nitrogen is present are
Cyanides and isocyanides Nomenclature In IUPAC system of nomenclature, cyanides are called as alkanenitriles. Methods of preparation Form alkyl halides When alkyl halide is treated with ethanolic solution of KCN, we get major product alkyl cyanide but when alkyl halide is treated with AgCN, the major product is alkyl isocyanide. RX + KCN (alcoholic) ————> RCN + KX alkyl halide RX + AgCN (alcoholic) ————> RNC + AgX Here CN- is nucleophile. The cyanide ion has an unshared pair of electrons on both carbon and nitrogen.
Molecular formula CH 3CN CH3-CH2-CN CH2=CH-CN C6H5CN CH3-CH-CN | CH 3
Here either carbon or nitrogen can act as a nucleophilic centre. Such a nucleophile which can react at two sites is known as an ambident nucleophile. NO2– is also an ambident nucleophile.
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AMINES 2 From acid amides Alkyl and aryl cyanides are prepared by dehydration of acid amides with phosphorous pentaoxide (P2O5) or thionyl chloride (SOCl2). In this method pure cyanide is prepared.
From diazonium salt Arenediazonium salt when reacted with a mixture of copper(1) cyanides and NaCN or KCN, lose nitrogen to give aryl cyanides
This method is a special case of Sandmeyer’s reaction. From aldoximes Dehydration of aldoxmies with P2O5 or acetic anhydride gives cyanide
From primary animes Isocyanides are obtained when primary amines are treated with CHCl3 in the persence of KOH.
The above reaction is also called carbylamine reaction. This reaction is not given by secondary and tertiary amines. Proparties of Cyanides and Isocyanides Physical properties The lower members of the family are colourless liquids and higher members are crystalline solid. Cyanides have generally pleasant odour but isocyanides have very disagreeable odour. Both - CN and - NC groups are highly polar. Both cyanides and isocyanides have high dipole moments resulting in strong intermolecular attraction and have relatively high boiling points. Alkyl cyanides have relatively high boiling point than the corresponding isomeric isocyanides. Alkyl cyanides are more soluble in water than alkyl isocyanides. The solubility of cyanides in water is due to their tendency to form hydrogen bonds with water molecules.
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AMINES
3
Chemical properties Hydrolysis Alkyl cyanides can be hydrolysed under acidic or basic condition to give amides. The further hydrolysis of amides give carboxylic acids and ammonia.
Iso cyanides can be hydrolysed by dilute acids to form primary amines and formic acid.
Alkyl isocyanides are not hydrolysed by alkalies. Reduction Nitriles undergo reduction to form primary amines as the product. We can use following reagents. a) H2 in the presence of Ni or Pt b) LiAlH4 c) Na + C2H5OH LiAlH4 CH3CH2CN ¾¾¾® CH3-CH2-CH2-NH2 propanamine
On the other hand isocyanides are reduced to secondry amines.
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AMINES 4 Addition reaction Isocyanides (but not cyanides) react with halogens, sulphur, mercuric oxide, ozone to give addition compounds.
Methyl Isocyanate gas (MIC) was responsible for the Bhopal gas tragedy. Isomerism Alkyl isocynides on heating for a long time rearrange to more stable alkyl cyanides. heat R - NC ¾¾¾® RCN alkyl isocyanide alkyl cyanide Uses 1) Ethane nitrile is used as a solvent in perfume industry. 2) Nitriles are also used in the manufacture of nitrile rubber and in textiles. 3) The alkyl nitriles or cyanides are useful intermediates in organic synthesis. Nitro compounds Nitro compounds are characterised by the presence of nitro group (-NO2) in their molecules. They may be aliphatic or aromatic. R-NO2 Ar-NO2 The - O-N=O group is isomeric with nitro group and is known as a nitrite group. Nomenclature They are named by using the prefix nitro before the name of parent hydrocarbon. CH3NO2 (Nitromethane) CH3CH2NO2 (Nitroethane)
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AMINES
5
Methods of preparation Alkyl bromides and alkyl iodides react with silver nitrite and give nitro compounds.
But with NaNO2 or KNO2 it gives ethyl nitrite.
NO2 is an ambident nucleophile (having two attacking sites N and O atoms). Attack through N gives nitroalkanes as product and attack through oxygen gives alkylnitrites. Alkali nitrites give alkyl nitrite. Due to ionic nature of alkali nitrites, the attack mostly occurs through oxygen because C-O bond is relatively stronger. In the case of silver nitrite which is covalent in nature, the attack mostly occurs through N atom giving nitro compound as major product.
By direct nitration Aromatic nitro compounds are obtained by this method. Nitrobenzene is produced when benzene is allowed to react with a mixture of conc. HNO3 and conc. H2SO4
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AMINES Mechanism of Nitration
6
Direct nitration of alkanes is relatively more difficult in comparison to the nitration of arenes. High temperature vapour phase reaction of alkanes with HNO3 gives a mixture of nitroalkanes and products like CO2, water and oxides of nitrogen.
Properties Physical properties Lower nitroalkanes are colourless liquids with pleasant smell. Aromatic nitro compounds like nitrobenzene have pale yellow colour. Nitrobenzene has a smell of bitter almonds. Nitroalkanes are sparingly soluble in water. Aromatic nitro compounds are not soluble in water at all. Nitro compounds are polar in nature so molecular interaction is more and they have high boiling points as compared to hydrocarbons of comparable molecular masses. Nitroalkanes are relatively more polar than their corresponding alkyl nitrite. C2H5NO2 C2H5 - O - N = O b.p. = 388 K b.p. = 261 K (nitro ethane) (ethyl nitrite) Chemical properties Reduction Nitroalkanes can be reduced to corresponding primary amines with LiALH4
Catalytic reduction Both aliphatic and aromatic nitro compounds are reduced to primary amines on reaction with H 2/Ni or H2/Pt or H2/Pd.
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AMINES 7 Reduction in acidic medium On reducing the nitro compounds with Zn/HCl, Fe/HCl or Sn/HCl, the NO2 group reduced to primary amino group. Fe/HCl CH3CH2NO2 + 6H ¾¾¾¾¾¾® CH3-CH2-NH2 + 2H20
Nitration By the nitration of nitrobenzene we get m-dinitrobenzene.
Sulphonation By sulphonation of nitrobenzene we get the following compound
Halogenation By the halogenation of nitrobenzene we get m-chloronitrobenzene.
Distinction between nitro alkanes and alkyl nitrites Nitroalkanes and alkyl nitrite are functional isomers having the structural formula
They can be distinguished by the following test, · Nitroalkanes on reduction with H2/Ni, Sn/HCl, or LiAlH4 give primary amines while nitrites give primary alcohols.
·
Alkyl nitrites on hydrolysis form alcohols while nitroalkanes do not get hydrolysed and form only salts.
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AMINES 8 · Nitroalkanes (primary and secondry) react with HNO2 give nitrolic acid which gives red colour with NaOH aqueous solution.
Ethyl nitrite does not give any color.
Uses · Lower nitroalkanes and nitrobenzene are widely used as industrial solvent for a large numbers of organic compounds. · These are used as intermediates in the production of explosives, pharmaceuticals etc. 2,4,6, trinitrotoulene (T.N.T.) and 1,3,5, trinitrobenzene (T.N.B.) are popular explosives. · Chloropicrin is used as insecticide · Nitroalkanes are used in the manufacture of hydroxylamine Amines Amines may be regarded as the alkyl or aryl derivatives of ammonia. They can be classified into primary, secondry, or tertiary amines.
Nomenclature According to IUPAC system primary amines are named as amino (-NH2) derivatives of the corresponding hydrocarbon and are called aminoalkanes. The secondry and tertiary amines are named as nitrogen substituted primary amine.
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AMINES 9 Preparation of amines When an aqueous or alcoholic solution of ammonia is heated with an alkyl halide at 373 K in a sealed tube, all the three types of amines are obtained. This type of react ion is called ammonolysis. CH 3I + NH3 ¾¾® CH3NH2 + HI CH3NH2 + CH3I ¾¾® CH3-NH-CH3 + HI CH3-NH + CH3I | CH3
¾¾® CH3-N-CH3 + HI
|
Amine formula CH3 NH 2 C2H 5NH 2 CH3-CH2-CH2 -CH 2-NH2 CH3-CH-CH3 | NH2 CH3-NH-CH3 CH3-N-CH3 | CH3 CH3-N-C2 H5 | CH3
CH3 Common name methylamine n propylamine isopropylamine dimethylamine trimethylamine
ethyldimethylamine
Tertiary amine also combine with methyl iodide to form quaternary ammonium salts. (CH3)3N + CH3I ¾¾® [(CH3)4N]+IThis mehtod is not suitable for the preparation of ovylamines. By Gabriel phthalimide synthesis In this method, phthalimide is first converted into potassium phthalimide by reaction with KOH. The potassium phthalimide on treatment with alkyl halide gives N-alkyl phthalimide which on hydrolysis with 20% HCl gives pure primary amine.
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AMINES
10
By the reduction of nitro compounds
Reduction on nitriles and Isonitriles Nitriles can be reduced to amines using H2/Ni or Pt, LiAlH4 or Na/C2H5OH
The reduction of isocyanides under similar condition give secondry amines
From amides
From amides using Hofmann degradation method By this method primary amide can be converted into primary amines.
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AMINES 11 By the reduction of oximes Primary amimes can be prepared by the reduction of oximes of aldehyde and ketones with Na/C2H5OH or LiAlH4
From alcohols (industrial method) On industrial scale aliphatic amines are prepared by passing vapours of alcohols and ammonia over alumina at 273 k.
The mixture of three amines are separated by fractional distillation. Preparatoin of aniline (industrial preparation) It is prepared by the following way
aniline is also prepared on large scale by treating chlorobenzene with ammonia at 473K and 60 atm. pressure using Cu2O as catalyst.
Properites Physical properties Among aliphatic amines the lower members are gases while higher members are liquids. Among oxylamines the lower members are liquids while higher members are solids. CH3NH2 and C2H5NH2 have ammonical smell but higher amines have fishy smell. Most of the aromatic amines are colourless in pure form. Aromatic amines
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AMINES 12 are generally toxic. All amines, except the tertiary amines are capable of forming intermolecular hydrogen bonds due to the presence of polar N-H bonds.
As a result of this, amines have higher boiling point than the non polar compounds of comparable molecular masses. Lower aliphatic amines are soluble in water. The higher one with larger alkyl groups are less soluble. Chemical properties Like ammonia, primary, secondry, tertiary amines all have a loan pair of electron on nitrogen atom. So they behave as a nucleophile and a base. Alkylamines are stronger base than ammonia because alkyl group is electron pumping group and they will increase the electron density on nitrogen.
C6H5NH2 will be less basic than ammonia because C6H5 group is electron attracting group and it will decrease the electron density on nitrogen. So CH3NH2 > NH3 > C6H5NH2 Basic strength of primary, secondry, tertiary amines
Among all the three amines the electron pumping effect (+I efect) is maximum in tertiary amines and least in primary amines. So on the basis of +I effect, the basic strength is expected to increase from primary amine to tertiary amine. This is true in gas phase. In aqueous medium, it is observed that basic character of secondry amine is maximum and tertiary amine have least basic character.
¾¾®
Basic character decreases
Explanation Basic strength in aqueous solution depends not only upon electron releasing effect but also upon steric and hydration effect. Steric effect Steric means hinderance by bulky group. If more and more groups are there, then there will be more steric effect. Suppose proton is going to attack on nitrogen atom in a amine, hinderance will be maximum in tertiary amine and so it will be least basic. Thus on the basis of steric effect we can say basic strength of Primary amine > Secondry amine > Tertiary amine or 1o > 2o > 3o Hydration effect uppose H+ is attacking on amine, we get the following protonated amine
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AMINES
13
The protonated amine forms hydrogen bond with water and release energy called hydration energy. Now greater the extent of H bonding, more will be its stabilisation and consequently greater will be the basic strength of the corresponding amine.
Hydration energy is maximum in primary amine (1o) and it is minimum in tertiary amine (3o). On the basis of hydration energy basic strength should decrease from 1o > 2o > 3o Thus, we find that in 3o amine, hydration is least and steric hinderance is maximum thus it is least basic inspite of maximum +I effect. In 1o amine (primary amine) steric - hinderance is least and hydration is maxium but +I effect is also minimum. Hence its basic strength is more than 3o amine. The resultant of all factors cause 2o amine to be still more basic than 1o amine thus overall basic strength varies as 2o > 1o > 3o or Secondry amine is more basic > Primary amine > Tertiary amine Reaction with acid Amines dissolve readily in acids to form quaternary salts
Salts of amines are ionic compounds. They are soluble in water. The amines, which are insoluble in water can be converted to the water soluble quaternary ammonium salts. Reaction with metal ions Lower aliphatic amines form co-ordination complexes with metal ions like Ag +, Cu2+. AgCl dissolves in
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AMINES methylamine solution.
14
Reaction with alkyl halides Amines react with alkyl halides to form amines of higher class +RX +RX +RX RNH 2 R 2NH R 3N ¾¾® ¾¾® -HX -HX tetra alkyl] ammonium halide C2H5NH2 + C2H5I ————> (C2H5)2NH + HI N-ethylamino ethane (C2H5)2NH + C2H5I ——————> (C2H5)3N + HI N,N-diethyl aminoethane (C 2H 5) 3N + C 2H 5I —————>
R 4N +X -
¾¾®
(C 2H 5) 4N
+
tetra ethylammonium iodide ' Reactron with acid chlorides and acid anhydrides Primary and secondry amines react with acid chlorides or acid anhydrides to form substituted amides. H | CH3-N-H + CH3COCl ——————> CH3-NHCOCH3 + HClN methylethaneamide
Tertiary amines do not undergo this reaction (acylation ) because they do not have H atom on the nitrogen.
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I-
AMINES 15 Benzoylation When H atom of amino group by benzoyl group (C6H5-CO) it is called benzoylation. Primary and secondry amines react with benzoyl chloride (C6H5COCl) in the presence of a base like pyridine to form benzoyl derivative.
Tertiary amines do not give this test. Reaction with HNO2 Primary aromatic amines react with HNO2 at low temperature (OoC) to give aromatic diazonium salts. This reaction is known as diazotisation
Primary aliphatic amines give alcohol NaNO2/HCl C2H5NH2 + HNO2 ¾¾¾¾¾¾® C2H5OH+N2 + H2O Secondary aliphatic and aromatic amines react with HNO2 to produce nitroso amines that are insoluble in the aqueous solution and comes out as a yellow oil and forms a separate layer.
Reaction with tertiary aliphatic amines (C2H5)3N + HNO2 ——————> [(C2H5)3NH] + NO2triethly ammonium nitrite Reaction with tertiary aromatic amines
Bromination of aniline We get 2,4,6, tribromo aniline
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AMINES 16 Sulphonation of aniline Aniline reacts with H2SO4(conc.) and forms anilinium hydrogen sulphate, which on heating gives p aminobenzene sulphonic acid which is also called sulphanilic acid.
Sulphanilic acid exists as zwitter ion ie a dipolar ion which exists in the form of internal salt structure. Diazonium salts and their reactions The diazonium salts are represented by ArN2+X-. They are prepared as under
The above reaction is known as diazotisation. Aromatic diazonium salts undergo a large numbers of reactions. The reaction of arenediazonium salts can be divided into two categories. (a) Substitution reaction (b) Coupling reaction Substitution reaction CuCl/HCl + ArN2 Cl ¾¾¾¾¾¾® ArCl + N2 CuBr/HBr + ArN2 Cl ¾¾¾¾¾¾® ArBr + N2 + ClCuCN/KCN + ArN2 Cl ¾¾¾¾¾¾® ArCN + N2 + ClThe above reactions are Sandmeyer’s reactions Cu/HCl + ArN2 Cl ¾¾¾¾¾¾® ArCl + N2 Cu/HBr] + Cl ArN ¾¾¾¾¾¾® ArBr + N2 + Cl2 The above reactions are Gattermann reaction Warm + ArN2 Cl + KI ¾¾¾¾¾¾® ArI + N2 + KCl HBF4 -Heat + + ArN2 Cl ¾¾¾¾¾¾® ArN2 BF4- ¾¾¾¾¾¾® ArF + N2 + BF3 Warm(H+) ArN2+Cl- + H2O ¾¾¾¾¾¾® ArOH + N2 + HCl
(flouroboric acid)
ArN2+Cl- + H3PO2 + HOH ¾¾¾¾¾¾® ArH + N2 + H3PO3 + HCl hypophosphorus acid arene Coupling reaction Diazonium salts react with highly activated aromatic compounds such as phenols and amines to form azo compounds. Azo compounds are coloured and many of them are used as dyes and indicator.
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AMINES Reaction with phenols
17
Reaction with aniline
The indicator methyl orange is obtained by coupling the diazonium salt of sulphanilic acid with N, Ndimethylaniline
Analysis of amines Hinsberg’s test This test helps to distinguish between primary, secondry and tertiary amines. The given amine is treated with benzene sulphonyl chloride in the presence of excess of aqueous KOH. · A clear solution in aqueous KOH which on acidification with HCl gives an insoluble material indicates primary amines.
·
A precipitate (insoluble compound) which is insoluble in KOH solution indicates secondry amine.
· Tertiary amines do not react with benzene sulphonyl chloride. An insoluble compound in KOH solution which dissolves by the addition of acid indicates tertiary amine.
Carbylamine test From this test we can identify primary amine (aliphatic as well as aromatic). In this test compound is warmed with CHCl3 (chloroform) in the presence of alcoholic solution of KOH. The primary amines yield isocyanides which have an extremely unpleasant smell. RNH2 + CHCl3 + 3KOH ¾¾¾¾¾¾® RNC + 3KCl + 3H2O alkyl isocyanide ArNH2 + CHCl3 + 3KOH ¾¾¾¾¾¾® ArNC + 3KCl + 3H2O aryl isocyanide
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AMINES
18
SOLVED PROBLEMS Q.1
Classify the following amines as primary, secondary and tertiary : N(CH3)2
NH2
(b)
(a)
Ans.
Q.2
Ans.
(c) (C2H5)2 CHNH2 (d) (C2H5)2NH (a) parimary (b) Tertiary (c) Primary (d) Secondary (a) Write structures of different isomeric amines corresponding to the molecular formula, C4H11N. (b) Write IUPAC names of all the isomers. (c) What type of ismerism is exhibited by different pairs of amines ? (a and b) Primary amines : (i) CH3CH2CH2CH2NH2 Butanamine
(ii) CH3CH2—CH—CH3 | NH2
Butan-2-amine
CH3 | CH 3—C—NH2 | CH3
(iii)
2-Methylpropan-2-amine
CH3
2|
3
1
(iv) CH3—CH—CH2—NH 2 2-Methylpropanamine
Secondary amines : (v) CH3—CH2—NH—CH2CH3 N-Ethylethanamine
(vi) CH3CH2CH2—NH—CH3 N-Methylpropanamine
1
CH3
3
2|
(vii) CH3—CH—NH—CH3 N-Methylpropan-2-amine
Tertiary amine : CH3 | (viii) CH3—N—CH2CH3 N, N-Dimethylethanamine
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AMINES (c)
19
Chain isomers : (i) & (iv), (ii) & (iii), (i) & (iii) Position isomers : (i) & (ii), (vi) & (vii) Metamers : (v) & (vi) Functional isomers : All primary amines are functional isomers of secondary and tertiary amines and vice versa.
Q.3
Give one chemical test to distinguish between the following pairs of compounds (i)
Methylamine and dimethylamine
(ii)
Secondary and tertiary amines
(iii) Ethylamine and aniline Ans.
(i)
These can be distinguished by the carbylamine test. Methylamine is 1° amine, therefore, it gives
carbylamine test, i.e., when heated with an alcholic solutoin of KOH and CHCl3, it gives an offensive smell of methyl carbylamine. In contrast, diethylamine is a secondary amine and hence does not give this test. CH3NH2 + CHCl3 + 3KOH Methylamine (1 o Amine)
Heat
CH3NC Methyl carbylamine (offensive smell)
(alc)
+ 3KCl + 3H2O (CH3CH2)2 NH
CHCl3/KOH(alc)
NO reaction.
Heat
Diethylamine (2o Amin)
(ii) These can be distinguished by Liebermann nitroamine test since secondary amines give Liebermann nitroamine test while tertiary amines do not. Secondry Amines on treatment with HNO2 (generated in situ by the action of HCl on NaNO2) gives yellow coloured oily N-nitrosoamine. For example. (CH3CH2)2 NH + HO—N=O
(CH 3CH 2) 2 N—N=O+H 2O
Diethy lamine
N-Nitrodiethylamine (Yellow colour)
N-Nitrosodiethylamine on warming with a crystal of phenol and conc. H2SO4, gives a great solution which when made alkaline with aqueous NaOH turns deep blue and then red on dilution. Tertiary amines do not give this test. (iii) Ethylamine is primary aliphatic amine while alinine is a primary aromatic amine. These may be distinguished by the azo dye test : Azo dye test : It involves the reaction of any aromatic primary amine with HNO2 (NaNO2+dil. HCl) at 273–278 K followed by treatment with an alkaline solution of 2-naphthol (b-naphthol) when a brilliant yellow, orange or red coloured dye is obtained. —NH2 + HONO + HCl
273-278 K
Benzenediazonium chloride
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AMINES
20 OH
OH +
Dil. NaOH pH 9-10
—N=N—
+ HCl
Benzenediazonium chloride
1-Phenylazo-2-naphthol (Orange dye)
2-Naphthol
Aliphatic primary amines under these conditions gives a brisk evolutoin of N 2 gas with the formation of primary alcohols, i.e., the solution remains clear. C2H 5NH2 + HONO
273-278 K
Ethylamine
C2H5OH + N2 + H2O Ethyl alcohol
These may be distinguished by the following test. Q.4
Ans.
Account for the following : (i) pKb of aniline is more than that of methylamine. (ii) Ethylamine is soluble in water, whereas aniline is not. (iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide. (iv) Although amino group is o- and p-directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m-nitroaniline. (i) In aniline, the lone pair of electrons on the N-atom are delocalized over the benzene ring. Resulting, electron density on the nitrogen decreases. On the other hand, in CH 3CH2. +ve-I-effect of CH3 increases the electron density on the N-atom. Thus, aniline is a weaker base than methylamine and hence its pKb value is higher than that of methylamine. (ii) Ethylamine dissolves in water because it forms H-bonds with water molecule as shown below.
H | H—N H—O | | C2H5 H
H | H—N H—O | | H C2H5
In aniline, due to the large, hydrocarbon part, the extent of H-bonding decreases considerably and hence aniline is insoluble in water. (iii) Methylamine being more basic than water, accepts a proton from water liberating OH– ions. CH3 NH2 + H—OH
+
CH3—NH3 + OH
–
These OH– ions combine with Fe3+ ions present in H2O to form brown precipitate of hydrated ferric oxide. FeCl3 ® Fe3+ + 3Cl– 2Fe3+ + 6OH– ® 2Fe(OH)3 or Fe2O3. 3H2O Hydrated ferric oxide (Brown ppt.)
(iv) Nitration is usually carried out with a mixture of conc. HNO3 and conc. H2SO4. In presence of these acids, most of aniline gets protonated to form anilinium ion. Thus, in presence of acids,
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AMINES the reaction mixture consists of aniline and anilinium ion. Now —NH 2
21
+
group in aniline is o, p-directing and activating while the NH 3 group in anilinium ion is m-directing and deactivating. On the other hand, nitration of aniline mainly gives p-nitroaniline, the nitration of anilinium ion gives mnitroaniline. NH2
NH2 +NH+2
NH2 NO2
+
+
–H Aniline
o-Nitroaniline (2%)
NO2 P-Nitroaniline(51%)
+
+
–H
+H +
+
NH3
NH3
NH2
+NH+2
NH4OH
+
–H
NO2
Anilinium ion
m-Nitroaniline
NO2 m-Nitroaniline(47%)
Thus, nitration of aniline gives a substantial amount of m-nitroaniline due to protonation of the amino group. Q.5
Ans.
Give plausible explanation for each of the following : (i) Why are amines less acidic than alcohols of comparable molecular masses ? (ii) Why are aliphatic amines stronger bases than aromatic amines ? (i) Loss of a proton from an amine gives amide ion while loss of a proton from alcohol gives an alkoxide ion as shown below : R — NH2 ® R — NHQ + H+ Amine
Amide ion
R — O — H ® R — OQ + H+ As O is more electronegative than N, RO– can accommodate the -ve charge more easily than the RNHQ can accommodate the -ve charge. As, ROQ is more stable than RNHQ . Therefore, amines are less acidic than alcohols. (ii) A liphatic amines are stronger bases than aromatic amines because : (a) due to resonance in aromatic amines, the lone pair of electrons on the nitrogen atom gets delocalised over the benzene ring and thus is less easily available for protonation. (b) The aryl amine ions have lower stability than the corresponding aryl amines. i.e., protonation of aromatic amines is not fovoured.
Q.6
Mention two important uses of sulphanilic acid.
Ans.
Sulphanilic acid is used in the manufacture of (i) dyes (ii) sulpha drugs.
Q.7
Aniline gets coloured on standing in air for a long time. Why ?
Ans.
Due to strong electron-donating effect (+R-effect) of NH2 group, the electron density on the benzene ring increases. As a result, aniline is easily oxidised on standing in air for a long time to form coloured products.
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AMINES
22
EXERCISE - I UNSOLVED PROBLEMS Q.1
Direct nitration of aniline is not carried out. Explain why.
Q.2
How can you control the reactivity of aniline in electrophilic substitution reaction ?
Q.3
Arrange the following in decreasing order of their basic strength : C6H5NH2, C2H5NH2, (C2H5)2NH, NH3
Q.4
Out of n-butylamine (Kb = 4.8) and isobutyl amine (Kb = 3) in aqueous medium, isbutylamine is more basic why ?
Q.5
Basic character of isobutylamine (Kb = 3), sec--butylamine (Kb = 4) and tert-butylamine (Kb = 5) in aqueous medium is in the order tert-Butylamine < sec-Butylamine < Isobutylamines. Why ?
Q.6
Predict, giving reasons, the order of basicity of the following compound in (i) gaseous phase (ii) in aqueous solutions ; (CH3)3N, (CH3)2NH, CH3NH2, NH3
Q.7
Account for the following : (a) Aniline does not undergo Friedel Crafts alkynation. (b) Although —NH2 group is ortho and paradirecting group nitration of aniline give along with ortho and para derivative, a good proportion of meta derivative also.
Q.8
How will you distinguish between (a) (b)
NH2
CH3—N—H
and CH3NH2,
and (CH3)3N.
CH3
Q.9
Classify the following amines as primary secondary or tertiary. NH2
(i)
N(CH3) 2
(ii)
(iii) (C2H5)2CHNH2 (iv) (C2H5)2NH. Q.10
(i) Write structures of different isomeric amines corresponding to the molecular formula C4H11N. (ii) Write IUPAC names of all the isomers. (iii) What type of isomerism is exhibited by different pairs of amines ?
Q.11
How will you convert (i) Benzene into aniline (ii) Benzene into N, N-dimethylaniline (iii) Cl—[CH2]4—Cl into hexane-1, 6-diamine.
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AMINES 23 Q.12 Write reactions of the final alkynation product of aniline with excess of methyl iodide in the presence of sodium carbonate solution. Q.13
Write chemical reaction of aniline with benzoyl chloride and write the name of the product obtained.
Q.14
Write structures of different isomers corresponding to the molecular formula C3H9N. Write IUPAC names of the isomers which will liberate nitrogen gas on treatment with nitrous acid.
Q.15
Give on chemical test to distinguish between the following pairs of compounds. (i) Methylamineand dimethylamine (ii) Secondary and tertiary amines (iii) Ethylamine and aniline (iv) Aniline and benzylamine (v) Aniline and N-methylaniline.
Q.16
How will you convert : (i) Ethanoic acid into methenamine, (ii) Hexanenitrile into 1-aminopentane, (iii) Methanol to ethanoic acid, (iv) Ethanamine into methanamine, (v) Ethanoic acid into propanoic acid, (vi) Methanamine into ethanamine (vii) Nitromethane into dimethylamine. (viii) Propanoic acid into ethanoic acid,
Q.17
Describe a method for the identification of primary secondary and tertiary amines. Also write chemical equations of the reactions involved.
Q.18
Write the IUPAC name of C6H5NHCH3
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AMINES
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EXERCISE - II BOARD PROBLEMS Q.1 Q.2 Q.3 Q.4 Q.5
Why do animes behave as nucleophiles ? [CBSE 2008] Why is an alkylamine more basic than ammonia [CBSE 2009] Arrange the following compounds in an increasing order of basic strengths in their aqueous solutions. NH3, CHNH2, (CH3)2NH, (CH3)3N [CBSE 2009] Arrange the following compound in an increasing order of their basic strength in aqueous solutions. NH3, RNH2, R2NH, R3N [CBSE 2009] Complete the following reaction equations : O
(i)
R—C—NH2
LiAlH4 H2O
(ii) C6H5N2Cl + H3PO2 + H2O (iii) C6H5NH2 + Br2(aq)
[CBSE 2009]
How are the following conversions carried out (i) Aniline to nitrobenzene (ii) Ethanamine to N-ethylethanamide (iii) Chloroethane to propan-1-amine
[CBSE 2009]
In the following cases rearrange the compound as directed : (i) In an increasing order of basic strength : C6H5NH2, C6H5N(CH3)2, (C2H5)2NH and CH3NH2 (ii) In a decreasing order of basic strength : Aniline, p-nitroaniline and p-toluidine (iii) In an increasing order of pKb values : C2H5NH2, C6H5NHCH3, (C2H5)2NH and CH6H5NH2
[CBSE 2010]
Q.8
Give chemical test to distinguish between C6H5CH2NH2 and C6H5NH2.
[CBSE 2010]
Q.9
Illustrate the following reactions giving a chemical equation in each case : (i) Gabriel phthanlimide synthesis (ii) A coupling reaction (iii) Hoffmann's bromamide reaction. (a) Explain why an alkylamine is more basic than ammonia. (b) How would you convert (i) Aniline to nitrobenzene (ii) Aniline to iodobenzene ?
Q.6
Q.7
Q.10
Q.11 Q.12 Q.13
[CBSE 2011]
[CBSE 2011]
Arrange the following compound in an increasing order of their solubility in water. C6H5NH2, (C2H5)2NH, C2H5NH2 [CBSE 2011] Rearrange the following in an increasing order of their basic strengths : C6H5NH2, C6H5N(CH3)2, (C6H5)2NH and CH3NH2 [CBSE 2011] Why is an alkylamine more basic than ammonia [CBSE 2011]
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AMINES Q.14 State reasons for the following : (i) pKb value for aniline is more than that for methylamine. (ii) Ethylamine is soluble in water whereas aniline is not soluble in water. (iii) Primay amines have higher boiling points than tertiary amines. Q.15
Q.16 Q.17
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A hydrocarbon 'A', (C4H8) on reaction with HCl gives a compound 'B', (C4H9Cl), which on reaction with 1 mol of NH8 gives compound 'C', (C4H11N). On reacting with NaNO2 and HCl followed by treatment with water, compound 'C' yields as optically active alcohol, 'D'. Ozonolysis of 'A' gives 2 moles of acetaldehyde. Identify compounds 'A' to 'D'. Explain the reactions involved. Write the structure of prop-2-en-1-amine. [CBSE 2013] Write the main products of the following reactions : (i)
CH3CH2NH2 O
?
S—Cl + N - C2H5
(ii)
O
N–H
(iii)
HNO2 0ºC
H
H
O
CH3–C–Cl Base
?
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[CBSE 2013]
